Lubricating compositions



Patented M... 22, 1938 UNITED" STATES. PATENT. OFFlCE 2,111,109 Gmll? ii -5113mm? Z...

signor to E. I. du Pont de Nemonrs & Company, Wilmington, Del., a. corporation of Delaware No Drawing. Application June 15, 1934,

Serial N0. 730,783

20 Claims.

This invention relates to the preparation of improved lubricating oils, and particularly to the preparation of new compositions of matter which eiiect improvements in certain qualities of lubrieating oils when added thereto.

Most of the lubricating oils used in the United States contain saturated paraflln hydrocarbon waxes as naturally occurring components. The presence oi these parafilns in limited quantities m imparts desirable qualities to the lubricating oils.

oil such as its viscosity-temperature character istics. Other more satisfactory methods of reducing the pour-point of lubricating oils have been developed. In general, they involve the addition of certaineompounds to the oils which permit the retention of the desirable parafflnic material but give the oils a low pour-point and exert a favorable influence on the viscosity-temperature characteristics. 13. S. Patent No. 1,815,022 is typical or several patents relating to-these pourpoint depressants.

This invention has as an object the production of high-grade lubricating oils having the object of the invention is the production of new compositions of matter which, in addition to oils suitable only i'or summer use, will transform them to products suitable also for winter use. Other objects will appear hereinafter.

These objects are accomplished by the following invention wherein a lubricating oil containing a solid waxy constituent in proportion suiilcient to give a relatively high pour-point, is blended with a high molecular weight ether containing material such as a dehydration condensation .mlymer oi octadecanediol, or a condensation product oi a chlorinated paraflin with an ether of a polycyclic phenol.

The process oi the present invention is illustrated in the examples given below which are not to be regarded as limitative. The standard *j oil reie'rred'toin the examples was a commercial heavy duty engine oil, representative of asumq 55 mer grade 011, and contained both paraflin wax desirable property of low pour-point. A further and petroleum wax. Its pour-point was 25 F. The pour-points outlined in thisspeciflcation were determined according to the procedure outlined in Technical Paper 323-A of the Bureau of Mines, p. 36 of the 1924 edition.

Ezample 1 To a solution of 13.5g. of the ethyl ether of betanaphthol in 19 g. of cyclohexane was added g. of anhydrous aluminum chloride. Considerable heat was developed, and the aluminum chloride turned black. The temperature. was

lowered to 35 0., and 90g. of chlorinated paraffin wax (12% chlorine) was stirfed in. Stirring was continuedior about 23 hours, after which the temperature was raised to 80'-85 0., .and held for one-half hour. There was considerable semi-solid material present, so 200 g. more of I cyclohexane was added to promote filtration The solution was in part decanted and in part filtered from the sludge. After a vacuum distillation to remove the solvent, there was obtained 44 g. of a waxy, heavy oil. Small quantities of the. product were added to the "standard oil" mentioned above to test its properties as apourpoint depressant.

Pour-point oi Percent by n n standardoil weight added (W -It will be apparent from the table that the condensation product is most efficient when added to the extent of 1%. Further additions continue to lower the pour-point, but only to a relatively small degree.

Example 2 I A high melting paramn or petroleum type wax, averaging '40 carbon 7 atoms per molecule was chlorinated to the mono-halide stage (7% chlorine) on a steam bath. Condensation of the chlorinated wax with alpha-naphthol methyl ether in cyclohexane, as described inExample 1, yield! ed a productxquite solid 'at room temperature.

One per cent of the material lowered the pour- 7 cycloliexane was condensed with 90 g. of the chloroparaffin above described, using aluminum chloride as the condensing agent. The product was a soft waxat room temperature. It was tested as a pour-point depressant without distilling oiT any residual chloroparamn. Two per cent of the crude material lowered the pour-point of the standard oil to F.

Earample 4 Forty-four grams of pure octaoecanediol and 0.3 g. of sodium hydroxide were heated at 235- 2'40" C. at 20 mm. pressure for 88 hours. The temperature was then raised to 260-275 C. and the heating continued under 15 mm. pressure for 76 hours. During the latter heating period samples were removed from time to time, and their pour-point depressant qualities tested. The following table shows the efiects of adding 1% of the octadecanediol condensation product to the standard oil.

Hours at Poubpoint 260 275 0. degrees F.

Example 5 Fifty grams of the crude products obtained by thehydrogenation of castor oil, and containing a substantial quantity of octadecanediol, was heated with 1.25 g. of sodium" hydroxide for 63.5 hours at .-260-275 C. and 13 mm. pressure; The condensation product when cool was a jelly-like, colorless solid. The following table indicates the efiects upon the pour-point of the standard oil obtained by the addition of various quantities of the condensation product.

. Percent of Pour-point of product standard oiladded degrees F.

In preparing the wax for the condensation, any

paraflln or petrolatum type wax, either pure or in the mixed state, maybe chlorinated. Thechlorination may be eifected by well-known methods,

preferably to the mono-halide stage, although itmay be carried further, if desired. Although condensation products of only three specific poly-,

cyclic phenol ethers'have beendescribed in the be used. To facilitate the condensation, a temperature of 30-40 C. is desirable, although room temperature may be employed with 8. correspondingly longer time; It is desirable to raise the temperature slowly to 80-100 0., after the 1880- tion subsides, not only to insure completion of the reaction, but to drive out hydrochloric acid vapors from the mixture. a

The condensation products prepared as described in the examples may, in some instances, ;contain unreacted chloro-paraflin and various by-products which are not active as pour-point depressants. The crude products may be used directly or the active material may be extracted with solvents such as ethylene dichloride, ethyl methyl ketone, acetone, etc. to obtain a more active product. It is to be noted that the pourpoint depressants of the present invention are high molecular weight ethers containing a plurality of aromatic nuclei and/ or ether groups.

The pour-point depressants of the present invention may be added to lubricating oils in any desirable proportion. 'Generally the preferred quantity for pour-point depression will be 0.25- 2.0%. Larger quantities may be used but are not in general economical.

The pour-point depressants of the present invention are valuable additions to the group of known pour-point depressants; The preparation of these depressants is, in general, practical and economical, and the process is of considerable technical and economic importance in view of the fact that by the use of such depressants lubricating oils may be made of utility within a wider range of temperature. I

The above description and examples are intended to be illustrative only. Any modification of or variation therefrom which conforms to the spirit of the invention is intended to be included within the scope of the claims.

I claim:

1. An improved lubricating oil comprising a viscous petroleum hydrocarbon fraction containing a solid waxy constituent in proportion suiilcient to give a relatively high pour-point blended with 0.25 to 2.0% of a high molecular weight ether condensation product containing a long aliphatic hydrocarbon chain.

2. An improved-lubricating oil comprising a. ,viscous petroleum hydrocarbon fraction containing a solid waxy constituent in proportion sufllcient to give a relatively high pour-point blended with 0.25 to 2.0% of a high molecular weight ether containing material of the class 1 consisting of octadecanedlol condensation polymers and condensation products of halogenated high molecucenes, and ethers of mono. and polyhydroxy diphenyls.

3. An improved lubricating oil comprising '9." viscous petroleum hydrocarbon fraction containing a solid waxy constituent in proportion sumcient to give a relatively high pour-point blended with 0.25 to 2.0% of a high molecular weight ether containing material obtained by the dehydration condensation of octadecanediol.

4. .An improved lubricating oil comprising a viscous petroleum hydrocarbon fraction containing a solid waxy constituent in proportion sufllcient to give a relatively high pour-point blended with 0.25 to 2.0% of octadecanediol condensation polymer. 1

5. An improved. lubricating oil comprising a viscous petroleum hydrocarbon fraction containing a solid waxy constituent in amount sufllcient to give a relatively high pour-point, blended with 0.25 to 2.0% oi! a high molecular weight ether containing material obtainable bythe condensation 01' chlorinated paraffln and methyl naphthyl ether.

6. A condensation product oi diphenylene-oxide and chlorinated paraffin'wax said'product being a viscous oil miscible with petroleum lubricating oils.

v "l. In the process for preparing materials resembling lubricating oils, the step comprising condensing a halogenated aliphatic hydrocarbon material having more than twelve carbon atoms,

with an aromatic ether or polyether in which the.

aromatic groups are hydrocarbon radicals havin at least one nuclear position available for condensation, in the presence of a condensing agent of the Friedel-Cratts type. v

8. A condensation product of a halogenated c hydrocarbon of high molecular weight and an ether of the general formula:

wherein R. is anaromatic hydrocarbon radical,

R is an aliphatic radical and R1 and R2 are each aromatic hydrocarbon radicals.

9. A condensation product of a chlorinated parafllnic hydrocarbon or high molecular weight and an ether of the general iormula:

. wherein R is an aromatic hydrocarbon radical,

R is an aliphatic radical andRr and R: are each aromatic hydrocarbon radicals.

10. A condensation product of diphenylene oxide and a halogenated paraflinic hydrocarbon material 01' high molecular weight.

11. A condensation product. of'diphenylene oxide and chlorinated paraflin wax.

12. Acondensation product of diphenylene oxide and chlorinated paramnic hydrocarbon mav terial of high molecular weight.

13. In the process for preparing materials resembling lubricating oils, the step comprising condensing a halogenated aliphatic hydrocarbon material oi" high molecular weight with an arcmatic ether in which the aromatic groups are vbon groups.

hydrocarbon radicals having at least onenuclear position available tor condensation in the presence of a condensing agent of the ,Friedel- Craits type 14. In the process for preparing materials resembling lubricatingoils, the step comprisingcondensing a chlorinated aliphatic hydrocarbon material of high molecular weight with an aromatic ether in which. the aromatic groups are hydrocarbon radicals having at least one nuclear position available for condensation in the pres-' ence of a condensing agent of the Friedel- Crafts type.

which comprises condensing a n wax with an aromatic ether 18. The proce chlorinated para of the formula:

wherein R1 and R2 are each aromatic hydrocarbon groups in the presence of aluminum chloride.

19. A'condensation product oi a chlorinated paraflln wax and an aromatic ether of the formula:

wherein R is an aromatic hydrocarbon radical and R is an aliphatic hydrocarbon group. 20. The process which comprises condensing a chlorinated paraflln wax with an aromatic ether of the: formula:

wherein R is an aromatic hydrocarbon radical and R is an aliphatic hydrocarbon group in the presence of aluminum chloride.

GEORGE DE WII'I GRAVES.

0| scLAl M-ER 2,lll,769.-Gcorgc De Witt Graces, W

11, Del. Luamcarmo- Courosrnons.

Patent dated March 22, 1938. laimer filed June 14, 1939, by the assignee,.E. I. du-Pont dc Ncmow's-and Company. Hereb enters this disclaimer as 1 0f ea'idapatent.

[5pm.- Gazette July 4, 1939.1

0.25 to 2.0% oi! a high molecular weight ether containing material obtainable bythe condensation 01' chlorinated paraffln and methyl naphthyl ether.

6. A condensation product oi diphenylene-oxide and chlorinated paraffin'wax said'product being a viscous oil miscible with petroleum lubricating oils.

v "l. In the process for preparing materials resembling lubricating oils, the step comprising condensing a halogenated aliphatic hydrocarbon material having more than twelve carbon atoms,

with an aromatic ether or polyether in which the.

aromatic groups are hydrocarbon radicals havin at least one nuclear position available for condensation, in the presence of a condensing agent of the Friedel-Cratts type. v

8. A condensation product of a halogenated c hydrocarbon of high molecular weight and an ether of the general formula:

wherein R. is anaromatic hydrocarbon radical,

R is an aliphatic radical and R1 and R2 are each aromatic hydrocarbon radicals.

9. A condensation product of a chlorinated parafllnic hydrocarbon or high molecular weight and an ether of the general iormula:

. wherein R is an aromatic hydrocarbon radical,

R is an aliphatic radical andRr and R: are each aromatic hydrocarbon radicals.

10. A condensation product of diphenylene oxide and a halogenated paraflinic hydrocarbon material 01' high molecular weight.

11. A condensation product. of'diphenylene oxide and chlorinated paraflin wax.

12. Acondensation product of diphenylene oxide and chlorinated paramnic hydrocarbon mav terial of high molecular weight.

13. In the process for preparing materials resembling lubricating oils, the step comprising condensing a halogenated aliphatic hydrocarbon material oi" high molecular weight with an arcmatic ether in which the aromatic groups are vbon groups.

hydrocarbon radicals having at least onenuclear position available tor condensation in the presence of a condensing agent of the ,Friedel- Craits type 14. In the process for preparing materials resembling lubricatingoils, the step comprisingcondensing a chlorinated aliphatic hydrocarbon material of high molecular weight with an aromatic ether in which. the aromatic groups are hydrocarbon radicals having at least one nuclear position available for condensation in the pres-' ence of a condensing agent of the Friedel- Crafts type.

which comprises condensing a n wax with an aromatic ether 18. The proce chlorinated para of the formula:

wherein R1 and R2 are each aromatic hydrocarbon groups in the presence of aluminum chloride.

19. A'condensation product oi a chlorinated paraflln wax and an aromatic ether of the formula:

wherein R is an aromatic hydrocarbon radical and R is an aliphatic hydrocarbon group. 20. The process which comprises condensing a chlorinated paraflln wax with an aromatic ether of the: formula:

wherein R is an aromatic hydrocarbon radical and R is an aliphatic hydrocarbon group in the presence of aluminum chloride.

GEORGE DE WII'I GRAVES.

0| scLAl M-ER 2,lll,769.-Gcorgc De Witt Graces, W

11, Del. Luamcarmo- Courosrnons.

Patent dated March 22, 1938. laimer filed June 14, 1939, by the assignee,.E. I. du-Pont dc Ncmow's-and Company. Hereb enters this disclaimer as 1 0f ea'idapatent.

[5pm.- Gazette July 4, 1939.1 

